Directed metalation linked to transition metal catalyzed cascade reactions: Two total syntheses of plicadin, the alleged coumestan from Psoralea plicata

Angewandte Chemie - International Edition

Volumn 38, Issue 10, 1999, Pages 1435-1438

  Chauder, Brian A ^a,b   Kalinin, Alexey V ^a   Taylor, Nicholas J ^a   Snieckus, Victor ^a,b  

^a UNIVERSITY OF WATERLOO   (Canada)

^b QUEEN S UNIVERSITY   (Canada)

Author keywords

Cross coupling; Domino reactions; Lithiation; Rearrangements; Total synthesis

Indexed keywords

CARBAMIC ACID; CHROMENE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; DATA ANALYSIS; STRUCTURE ACTIVITY RELATION;

EID: 0033577824     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990517)38:10<1435::AID-ANIE1435>3.0.CO;2-B     Document Type: Article

References (26)

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2. Structure 1 is a member of the large and bioactivity-rich class of naturally occurring coumestans: a) W. Stadibauer, T. Kappe, Heterocycles 1993, 35, 1425-1440;
3. b) J. D. Hepworth in Comprehensive Heterocyclic Chemistry, Vol. 4 (Ed.: A. R. Katritzky), Pergamon, New York, 1984, pp. 995-998;
4. c) F. M. Dean in The Total Synthesis of Natural Products, Vol. 1 (Ed.: J. ApSimon), Wiley, New York, 1973, pp. 485-548;
5. d) A. Mustafa in The Chemistry of Heterocyclic Compounds, Vol. 23 (Ed.: A. Weissberger), Wiley, New York, 1967, pp. 243-255.
6. a) V. Snieckus, Chem. Rev. 1990, 90, 879-933;
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12. g) for application of this remote anionic Fries reaction to the synthesis of gilvocarcins, see C. A. James, V. Snieckus, Tetrahedron Lett. 1997, 38, 8149-8152, and for its generalization to arylfuryl and arylthiophenyl for construction of coumestans,
13. see C. A. James, PhD thesis, University of Waterloo (Canada), 1998.
14. For further scope of this two-step procedure in the synthesis of 4-hydroxycoumarins, some of which are inaccessible by classical Friedel - Crafts and Lewis acid catalyzed Fries rearrangement reactions, see A. V. Kalinin, A. J. M. da Silva, C. C. Lopes, R. S. C. Lopes, V. Snieckus, Tetrahedron Lett. 1998, 39, 4995-4998;
15. A. V. Kalinin, V. Snieckus, Tetrahedron Lett. 1998, 39, 4999-5002.
16. B. A. Chauder, C. C. Lopes, R. S. C. Lopes, A. J. M. da Silva, V. Snieckus, Synthesis 1998, 279-282, and references therein.
17. K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. 1975, 4467-4470.
18. Prepared according to D. E. Janssen, C. V. Wilson, Org. Synth. Coll. Vol. IV 1963, 547-549.
19. a) R. D. Stephens, C. E. Castro, J. Org. Chem. 1963, 28, 3313-3315;
20. b) C. E. Castro, E. J. Gaughan, D. C. Owsley, J. Org. Chem. 1966, 31, 4071-4078;
21. c) for a survey of palladium-based routes to benzofurans, see R. C. Larock, E. D. Yum, M. J. Doty, K. K. C. Sham, J. Org. Chem. 1995, 60, 3270-3271.
22. 3, EtSNa, or LiCl, the corresponding methyl ether of 11 did not afford plicadin but gave product mixtures, indicating chromene and lactone ring opening.
23. Prepared according to F. E. King, K. G. Neill, J. Chem. Soc. 1952, 4752-4756;
24. also see J. O. Amupitan, Synthesis 1983, 730, and references therein.
25. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-101777. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
26. 13C NMR data from the authors.